CN114181526A - Selective laser sintering elastic nano particle composite nylon powder and preparation method thereof - Google Patents
Selective laser sintering elastic nano particle composite nylon powder and preparation method thereof Download PDFInfo
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- 239000004677 Nylon Substances 0.000 title claims abstract description 126
- 229920001778 nylon Polymers 0.000 title claims abstract description 126
- 239000000843 powder Substances 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 238000000110 selective laser sintering Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 16
- 239000002245 particle Substances 0.000 claims abstract description 124
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 239000007822 coupling agent Substances 0.000 claims abstract description 43
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000001816 cooling Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 229920000459 Nitrile rubber Polymers 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000012783 reinforcing fiber Substances 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 16
- 239000003365 glass fiber Substances 0.000 claims description 16
- 229920003043 Cellulose fiber Polymers 0.000 claims description 15
- 229920006152 PA1010 Polymers 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 15
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010456 wollastonite Substances 0.000 claims description 15
- 229910052882 wollastonite Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- SPIPLAVUQNWVMZ-UHFFFAOYSA-N (2,4-ditert-butylphenoxy)-fluorophosphinous acid Chemical compound CC(C)(C)C1=CC=C(OP(O)F)C(C(C)(C)C)=C1 SPIPLAVUQNWVMZ-UHFFFAOYSA-N 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- SHXZLWBBEAWQJP-UHFFFAOYSA-N dihydroxyphosphanyl [2,3,5,6-tetrakis(2,4-ditert-butylphenyl)-4-phenylphenyl] hydrogen phosphite Chemical compound CC(C)(C)C1=CC(=C(C=C1)C2=C(C(=C(C(=C2C3=C(C=C(C=C3)C(C)(C)C)C(C)(C)C)OP(O)OP(O)O)C4=C(C=C(C=C4)C(C)(C)C)C(C)(C)C)C5=C(C=C(C=C5)C(C)(C)C)C(C)(C)C)C6=CC=CC=C6)C(C)(C)C SHXZLWBBEAWQJP-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 2, 4-di-tert-butylphenyl Chemical group 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Abstract
The invention discloses selective laser sintering elastic nanoparticle composite nylon powder, which comprises the following raw materials in parts by weight: 60-90 parts of nylon, 5-20 parts of nano elastic particles, 5-30 parts of reinforced fibers, 0.1-2 parts of composite antioxidant, 0.2-3 parts of flow assistant and 1-5 parts of coupling agent; compared with the traditional nylon sintered product, the elastic nano particle composite nylon powder not only enhances the tensile strength, but also improves the impact strength, improves the toughness of the material, improves the strength of the nylon laser sintered product and simultaneously improves the brittleness of the nylon laser sintered product, thereby increasing the application scene of the selective laser sintered nylon.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to elastic nanoparticle composite nylon powder for selective laser sintering and a preparation method thereof.
Background
Selective Laser Sintering (SLS) technology uses an infrared laser (e.g., CO2 laser and fiber laser) as an energy source, and laser beams are selectively sintered under the control of a computer according to layered cross-sectional information during processing, and sintering of the next layer is performed after one layer is completed. Nylon is the most used plastic powder in the current laser selective sintering technology, and the tensile strength and the impact strength of a sintered part are low, so that the application of the nylon in engineering is seriously influenced.
In order to improve the mechanical strength of nylon products, the nylon reinforced powder is generally prepared by adding carbon fibers, glass beads, graphene and the like. For example, patent CN102337021B discloses a nylon composite powder material for selective laser sintering. The patent adopts a mechanical mixing method, and prepares mixed nylon powder by adding glass beads, a flow aid and a coupling agent. CN101036944A discloses a preparation method of a nylon coated metal powder material, which comprises heating a mixture of nylon resin, a solvent, metal powder and an antioxidant in a closed container to gradually bond and coat nylon on the surface of metal particles with the metal particles as cores, and finally depositing nylon-coated metal composite powder. CN111393841A discloses a preparation method of graphene nylon powder, which comprises the steps of adding nano-graphene, nylon salt, a molecular weight regulator and deionized water into a reaction kettle, cooling, bracing, discharging and dicing through polymerization reaction to prepare low-molecular-weight nano-graphene composite nylon powder, adding graphene nylon granules and high-molecular-weight nylon granules into a powder preparation kettle, preparing graphene nylon powder through a solvent method, and finally mixing and screening the graphene nylon powder, the nano-graphene nylon powder, a flow assistant and an antioxidant. These methods all improve the tensile strength and tensile modulus of the nylon powder sintered product to some extent, but do not improve the brittleness of the material.
Disclosure of Invention
In view of the above, the present invention aims to provide an elastic nanoparticle composite nylon powder for selective laser sintering and a preparation method thereof, which can improve the strength of a nylon laser sintered product and simultaneously improve the brittleness of the nylon laser sintered product.
The invention relates to selective laser sintering elastic nanoparticle composite nylon powder, which comprises the following raw materials in parts by weight: 60-90 parts of nylon, 5-20 parts of nano elastic particles, 5-30 parts of reinforced fibers, 0.1-2 parts of composite antioxidant, 0.2-3 parts of flow assistant and 1-5 parts of coupling agent;
further, the composite nylon powder comprises the following raw materials in parts by weight: 75 parts of nylon, 15 parts of nano elastic particles, 15 parts of reinforcing fibers, 0.1 part of composite antioxidant, 1 part of flow aid and 3 parts of coupling agent;
further, the nylon is one or a mixture of more than two of PA6, PA12, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA 1212; the nano elastic particles are one or a mixture of more than two of nitrile rubber powder, POE particles and SBS particles;
further, the reinforced fiber is one or a mixture of more than two of glass fiber, carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber;
further, the fiber particle size is 10-60 μm;
further, the compound antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants;
further, the hindered phenol antioxidant is one or two of 1,3, 5-trimethyl-2, 4,6, -tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol; the phosphite antioxidant is one or two of 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylyl diphosphite;
further, the flow assistant is one or a mixture of more than two of gas-phase silicon dioxide, gas-phase aluminum oxide and nano titanium dioxide; the coupling agent is one or a mixture of more than two of KH550, KH560, KH570, KH792 and DL 602.
The invention also discloses a preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering, which comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, adjusting the pH value to 3-7, stirring at 20-50 ℃ for 30-150min, adding nano elastic particles to prepare a hydrolysis mixture, adding absolute ethyl alcohol, stirring at 50-150r/min for 1-3h, and finally drying at 30-80 ℃; preparing modified nano elastic particles;
b. mixing nylon powder and a solvent, stirring for 20-40min at the temperature of 90-110 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 10-20min, vacuumizing, introducing inert gas, heating to 130-210 ℃ at the heating rate of 1-3 ℃/min, and preserving heat for 0.5-2h after the temperature reaches a set temperature; after the heat preservation time is up, cooling to a set temperature according to the cooling rate of 2-4 ℃/min, finally adding the reinforced fiber, stirring for 0.5-1.5h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder with a flow aid by using a ball mill to prepare the nano elastic particle composite nylon powder;
further, in the step a, the volume ratio of the absolute ethyl alcohol to the deionized water is 8:1-2:1, and the volume ratio of the coupling agent to the mixture of the absolute ethyl alcohol and the deionized water is 1:2-1: 10; adding absolute ethyl alcohol into the hydrolysis mixture according to the volume ratio of 1:20-1: 80.
The invention has the beneficial effects that: according to the elastic nano particle composite nylon powder for selective laser sintering and the preparation method thereof, compared with a traditional nylon sintered product, after the elastic nano particle composite nylon powder is subjected to selective laser sintering, the tensile strength is enhanced, the impact strength is improved, the toughness of the material is improved, the strength of the nylon laser sintered product is improved, and the brittleness of the nylon laser sintered product is improved, so that the application scene of selective laser sintering nylon is increased. According to the invention, the nano elastic particles are modified by the coupling agent, then the modified nano elastic particles, nylon and the like are added into a reaction kettle, the temperature rising and reducing rate is controlled by a solvent method to prepare the composite nylon suspension liquid with the nano particles as the inner core, the reinforcing fiber is added, and then the temperature reduction is carried out to prepare the composite nylon powder with the nano particles as the inner core, wherein the nano particles coated with the film on the surface of the reinforcing fiber.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example one
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 60 parts of nylon, 5 parts of nano elastic particles, 20 parts of reinforcing fibers, 0.5 part of composite antioxidant, 0.2 part of flow aid and 1 part of coupling agent.
In the embodiment, the nylon is PA1212, and in the embodiment, the PA1212 is replaced with one of PA12, PA11, PA66, PA610, PA612, PA1010, PA1012, and PA6, or replaced with a mixture of PA1212, PA12, PA11, PA66, PA610, PA612, PA1010, PA1012, and PA6, all of which are in equal parts by weight, so that qualified products are obtained.
In the embodiment, the nano elastic particles are nitrile rubber powder, and in the embodiment, the nitrile rubber powder is replaced by one of POE particles and SBS particles or replaced by a mixture of the nitrile rubber powder, the POE particles and the SBS particles according to the same weight part, so that qualified products are obtained.
In this embodiment, the reinforcing fiber is glass fiber, and in this embodiment, the glass fiber is replaced by one of carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber or a mixture of glass fiber, carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber in the same weight parts, so as to obtain qualified products.
In this example, the fiber particle size was 10 μm.
In this example, the hindered phenol antioxidant is 1,3, 5-trimethyl-2, 4,6, -tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; the phosphite antioxidant is 2' -ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite.
In the embodiment, the flow aid is fumed silica, and in the embodiment, the fumed silica is replaced by one of fumed alumina and nano titanium dioxide or a mixture of the fumed silica, the fumed alumina and the nano titanium dioxide according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is KH550, and in the embodiment, KH550 is replaced by one of KH560, KH570, KH792 and DL602 or a mixture of KH550 and KH560, KH570, KH792 and DL602 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 3 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 8:1 (volume ratio), coupling agent: stirring a mixture of absolute ethyl alcohol and deionized water at a volume ratio of 1:2 at a temperature of 20 ℃ for 30min, adding the nano elastic particles to prepare a hydrolyzed mixture, then adding the absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to the volume ratio of 1:20, stirring for 1h at a stirring speed of 50r/min, finally placing the stirred nano elastic particles in a vacuum drying oven for drying, and setting the drying temperature at 30 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and a solvent methanol into a reaction kettle, mixing, stirring at 90 ℃ for 20min, adding the modified nano elastic particles and the composite antioxidant, stirring for 10min, vacuumizing, introducing inert gas, heating to 170 ℃ at the heating rate of 1 ℃/min, and keeping the temperature and the pressure for 1h after the set temperature is reached; after the heat preservation time is up, cooling to 110 ℃ at the cooling rate of 2 ℃/min, keeping the constant temperature for 1h, further cooling to 80 ℃, finally adding the reinforced fiber, stirring for 0.5h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
Example two
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 90 parts of nylon, 20 parts of nano elastic particles, 30 parts of reinforcing fibers, 2 parts of composite antioxidant, 3 parts of flow aid and 3 parts of coupling agent.
In the embodiment, the nylon is PA12, and in the embodiment, PA12 is replaced by one of PA6, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA1212, or replaced by a mixture of PA12 and PA6, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA1212, all of which are qualified products.
In the embodiment, the nano elastic particles are POE particles, and in the embodiment, the POE particles are replaced by one of nitrile rubber powder and SBS particles or a mixture of the POE particles, the nitrile rubber powder and the SBS particles according to the same weight part, so that qualified products are obtained.
In the embodiment, the reinforcing fiber is carbon fiber, and in the embodiment, the carbon fiber is replaced by one of glass fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber or a mixture of the carbon fiber, the glass fiber, the needle-shaped wollastonite, the silicon carbide and the cellulose fiber according to the same weight part, so that qualified products are obtained.
In this example, the fiber particle size was 60 μm.
In this embodiment, the hindered phenol antioxidant is 2, 6-di-tert-butyl-4-methyl-phenol; the phosphite antioxidant is tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylyl diphosphite.
In the embodiment, the flow assistant is fumed alumina, and the fumed alumina is replaced by one of fumed silica and nano titanium dioxide or a mixture of fumed alumina, fumed silica and nano titanium dioxide according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is KH560, and in the embodiment, KH560 is replaced by one of KH550, KH570, KH792 and DL602 or a mixture of KH560 and KH550, KH570, KH792 and DL602 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 7 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 2:1 (volume ratio), coupling agent: stirring the mixture of absolute ethyl alcohol and deionized water at a volume ratio of 1:10 at 50 ℃ for 150min, adding the nano elastic particles to prepare a hydrolyzed mixture, then adding absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to a volume ratio of 1:80, stirring for 3h at a stirring speed of 150r/min, finally placing the stirred nano elastic particles in a vacuum drying oven for drying, and setting the drying temperature at 80 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and solvent ethanol into a reaction kettle, mixing, stirring for 40min at the temperature of 110 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 20min, vacuumizing, introducing inert gas, heating to 170 ℃ at the heating rate of 3 ℃/min, and preserving heat and pressure for 2h after the set temperature is reached; after the heat preservation time is up, cooling to 130 ℃ according to the cooling rate of 4 ℃/min, keeping the constant temperature for 1h, further cooling to 100 ℃, finally adding the reinforced fiber, stirring for 1.5h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
EXAMPLE III
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 60 parts of nylon, 20 parts of nano elastic particles, 5 parts of reinforcing fibers, 1 part of composite antioxidant, 0.2 part of flow aid and 3 parts of coupling agent.
In the embodiment, the nylon is PA1010, and in the embodiment, the PA1010 is replaced by one of PA12, PA6, PA66, PA610, PA612, PA11, PA1012 and PA1212, or replaced by a mixture of PA1010, PA12, PA6, PA66, PA610, PA612, PA11, PA1012 and PA1212, and qualified products are obtained.
In the embodiment, the nano elastic particles are SBS particles, and in the embodiment, the SBS particles are replaced by one of POE particles and nitrile rubber powder or replaced by a mixture of the SBS particles, the POE particles and the nitrile rubber powder according to the same weight part, so that qualified products are obtained.
In the embodiment, the reinforcing fiber is needle-shaped wollastonite, and the needle-shaped wollastonite is replaced by one of carbon fiber, glass fiber, silicon carbide and cellulose fiber or a mixture of the needle-shaped wollastonite and the carbon fiber, the glass fiber, the silicon carbide and the cellulose fiber according to the same weight part, so that qualified products are obtained.
In this example, the fiber particle size was 20 μm;
in this example, the hindered phenol antioxidant is 1,3, 5-trimethyl-2, 4,6, -tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol; the phosphite antioxidant is 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphite.
In the embodiment, the flow assistant is nano titanium dioxide, and in the embodiment, the nano titanium dioxide is replaced by one of fumed alumina and fumed silica or a mixture of the nano titanium dioxide, the fumed alumina and the fumed silica according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is KH570, and in the embodiment, KH570 is replaced by one of KH560, KH550, KH792 and DL602 or a mixture of KH570 and KH560, KH550, KH792 and DL602 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 4 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 3:1 (volume ratio), coupling agent: stirring a mixture of absolute ethyl alcohol and deionized water at a volume ratio of 1:3 at a temperature of 25 ℃ for 40min, adding the nano elastic particles to prepare a hydrolyzed mixture, then adding the absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to a volume ratio of 1:30, stirring for 2h at a stirring speed of 70r/min, finally placing the stirred nano elastic particles in a vacuum drying oven for drying, and setting the drying temperature at 40 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and solvent ethanol into a reaction kettle, mixing, stirring for 25min at the temperature of 100 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 13min, vacuumizing, introducing inert gas, heating to 160 ℃ at the heating rate of 2 ℃/min, and keeping the temperature and the pressure for 1.5h after the set temperature is reached; after the heat preservation time is up, cooling to 115 ℃ according to the cooling rate of 3 ℃/min, keeping the constant temperature for 1h, further cooling to 85 ℃, finally adding the reinforced fiber, stirring for 0.7h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
Example four
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 90 parts of nylon, 5 parts of nano elastic particles, 30 parts of reinforcing fibers, 0.5 part of composite antioxidant, 3 parts of flow aid and 1 part of coupling agent.
In the embodiment, the nylon is PA66, and in the embodiment, PA66 is replaced by one of PA12, PA11, PA6, PA610, PA612, PA1010, PA1012 and PA1212, or replaced by a mixture of PA66PA6 and PA12, PA11, PA6, PA610, PA612, PA1010, PA1012 and PA1212, all of which are in equal parts by weight, so that qualified products are obtained.
In the embodiment, the nano elastic particles are nitrile rubber powder, and in the embodiment, the nitrile rubber powder is replaced by one of POE particles and SBS particles or replaced by a mixture of the nitrile rubber powder, the POE particles and the SBS particles according to the same weight part, so that qualified products are obtained.
In this embodiment, the reinforcing fiber is silicon carbide, and in this embodiment, silicon carbide is replaced by one of carbon fiber, needle-shaped wollastonite, glass fiber and cellulose fiber or by a mixture of silicon carbide and carbon fiber, needle-shaped wollastonite, glass fiber and cellulose fiber in the same weight parts, so as to obtain acceptable products.
In this example, the fiber particle size was 30 μm;
in this example, the hindered phenol antioxidant is 1,3, 5-trimethyl-2, 4,6, -tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; the phosphite antioxidant is 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphite.
In the embodiment, the flow aid is fumed silica, and the fumed silica is replaced by one of fumed alumina and nano titanium dioxide or a mixture of fumed silica, fumed alumina and nano titanium dioxide according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is KH792, and in the embodiment, KH792 is replaced by one of KH560, KH570, KH550 and DL602 or a mixture of KH792 and KH560, KH570, KH550 and DL602 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 5 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 4: 1 (volume ratio), coupling agent: stirring a mixture of absolute ethyl alcohol and deionized water at 35 ℃ for 80min to prepare a hydrolysis mixture, adding absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to the volume ratio of 1:50, stirring for 2h at the stirring speed of 100r/min, and finally, placing the stirred nano elastic particles in a vacuum drying oven for drying, wherein the drying temperature is set at 50 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and a solvent methanol into a reaction kettle, mixing, stirring for 30min at the temperature of 105 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 15min, vacuumizing, introducing inert gas, heating to 130 ℃ at the heating rate of 2 ℃/min, and keeping the temperature and the pressure for 1h after the set temperature is reached; after the heat preservation time is up, cooling to 120 ℃ according to the cooling rate of 2 ℃/min, keeping the constant temperature for 1h, further cooling to 90 ℃, finally adding the reinforced fiber, stirring for 1h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and has elastic particles as an inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
EXAMPLE five
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 80 parts of nylon, 10 parts of nano elastic particles, 25 parts of reinforcing fibers, 1 part of composite antioxidant, 2 parts of flow aid and 1 part of coupling agent.
In the embodiment, the nylon is PA12, and in the embodiment, PA610 is replaced by one of PA12, PA11, PA66, PA6, PA612, PA1010, PA1012 and PA1212, or replaced by a mixture of PA610 and PA12, PA11, PA66, PA6, PA612, PA1010, PA1012 and PA1212, all of which are qualified products.
In the embodiment, the nano elastic particles are nitrile rubber powder, and in the embodiment, the nitrile rubber powder is replaced by one of POE particles and SBS particles or replaced by a mixture of the nitrile rubber powder, the POE particles and the SBS particles according to the same weight part, so that qualified products are obtained.
In this embodiment, the reinforcing fiber is a cellulose fiber, and in this embodiment, the cellulose fiber is replaced by one of carbon fiber, needle-shaped wollastonite, silicon carbide and glass fiber, or a mixture of the cellulose fiber, the carbon fiber, the needle-shaped wollastonite, the silicon carbide and the glass fiber in the same weight part, so as to obtain a qualified product.
In this example, the fiber particle size was 30 μm;
in this example, the hindered phenol antioxidants are 1,3, 5-trimethyl-2, 4,6, -tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol; the phosphite antioxidant is 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphite.
In the embodiment, the flow aid is fumed silica, and the fumed silica is replaced by one of fumed alumina and nano titanium dioxide or a mixture of fumed silica, fumed alumina and nano titanium dioxide according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is DL602, and in the embodiment, the DL602 is replaced by one of KH560, KH570, KH792 and KH550 or a mixture of DL602 and KH560, KH570, KH792 and KH550 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 6 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 6: 1 (volume ratio), coupling agent: stirring a mixture of absolute ethyl alcohol and deionized water at 45 ℃ for 140min, adding the nano elastic particles to prepare a hydrolyzed mixture, then adding the absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to the volume ratio of 1:70, stirring for 1h at the stirring speed of 135r/min, finally placing the stirred nano elastic particles in a vacuum drying oven for drying, and setting the drying temperature at 70 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and solvent ethanol into a reaction kettle, mixing, stirring for 25min at the temperature of 110 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 18min, vacuumizing, introducing inert gas, heating to 160 ℃ at the heating rate of 3 ℃/min, and keeping the temperature and the pressure for 1h after the set temperature is reached; after the heat preservation time is up, cooling to 115 ℃ according to the cooling rate of 4 ℃/min, keeping the constant temperature for 1h, further cooling to 95 ℃, finally adding the reinforced fiber, stirring for 1.2h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
EXAMPLE six
The elastic nano particle composite nylon powder for selective laser sintering comprises the following raw materials in parts by weight: 75 parts of nylon, 15 parts of nano elastic particles, 15 parts of reinforcing fibers, 0.1 part of composite antioxidant, 1 part of flow aid and 3 parts of coupling agent.
In the embodiment, the nylon is PA6, and in the embodiment, PA1212 is replaced by one of PA12, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA1212, or replaced by a mixture of PA6, PA12, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA1212, and qualified products are obtained.
In the embodiment, the nano elastic particles are POE particles, and in the embodiment, the POE particles are replaced by one of nitrile rubber powder and SBS particles or a mixture of the POE particles, the nitrile rubber powder and the SBS particles according to the same weight part, so that qualified products are obtained.
In this embodiment, the reinforcing fiber is glass fiber, and in this embodiment, the glass fiber is replaced by one of carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber or a mixture of glass fiber, carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber in the same weight parts, so as to obtain qualified products.
In this example, the fiber particle size was 40 μm;
in this example, the hindered phenol antioxidant is 1,3, 5-trimethyl-2, 4,6, -tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; the phosphite antioxidant is 2' -ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite.
In the embodiment, the flow assistant is fumed alumina, and the fumed alumina is replaced by one of fumed silica and nano titanium dioxide or a mixture of fumed alumina, fumed silica and nano titanium dioxide according to the same weight part, so that qualified products are obtained.
In the embodiment, the coupling agent is KH550, and in the embodiment, KH550 is replaced by one of KH560, KH570, KH792 and DL602 or a mixture of KH550 and KH560, KH570, KH792 and DL602 according to the same weight parts, so that qualified products are obtained.
The preparation method of the elastic nanoparticle composite nylon powder by selective laser sintering comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, and adjusting the pH value to be 6 by adopting glacial acetic acid and ammonia water, wherein the weight ratio of absolute ethyl alcohol: deionized water 7: 1 (volume ratio), coupling agent: stirring a mixture of absolute ethyl alcohol and deionized water at 45 ℃ for 140min, adding the nano elastic particles to prepare a hydrolyzed mixture, then adding the absolute ethyl alcohol into the hydrolyzed mixture of the coupling agent and the nano elastic particles according to the volume ratio of 1:50, stirring for 2h at the stirring speed of 100r/min, finally placing the stirred nano elastic particles in a vacuum drying oven for drying, and setting the drying temperature at 50 ℃ to prepare modified nano elastic particles;
b. adding nylon powder and a solvent dimethylformamide into a reaction kettle, mixing, stirring for 30min at the temperature of 100 ℃, then adding modified nano elastic particles and a composite antioxidant, stirring for 15min, vacuumizing, introducing inert gas, heating to 200 ℃ at the heating rate of 2 ℃/min, and preserving heat and pressure for 1.5h after the set temperature is reached; after the heat preservation time is up, cooling to 120 ℃ according to the cooling rate of 3 ℃/min, keeping the constant temperature for 1h, further cooling to 90 ℃, finally adding the reinforced fiber, stirring for 1h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and has elastic particles as an inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
Comparative example: compared with the nano elastic particle composite nylon powder, the nano elastic particles are not used in the preparation of the powder, and other implementation steps and the using amount are the same as those of the two examples.
The mechanical property test standard of the invention is as follows:
test standards for tensile properties and elongation at break: GB/T1447 & lt 2005 & gt New Enhance of fiber reinforced Plastic tensile Performance test method-
Impact strength test standard: GB/T1843-2008 plastic cantilever beam impact strength determination
In order to show the difference in performance between the nano-elastic particle composite nylon powder and the conventional nylon powder obtained by the method of the present invention, tensile test specimens and notched impact test specimens were prepared using the nano-elastic particle composite nylon powder and the conventional nylon powder, respectively, using a selective laser sintering apparatus, and then comparative tests, which are referred to as examples in the present invention, were performed.
The nylon powders prepared by the examples and the comparative examples were used to prepare standard tensile test bars and standard notched impact test bars by using a selective laser sintering apparatus, and the overall properties of the above examples and comparative examples were counted by testing, and the results were as follows:
as can be seen from the test results of the second embodiment, the fifth embodiment and the comparative example, the nano elastic particle composite nylon powder prepared by the invention can greatly improve the impact strength of the nylon powder and greatly increase the toughness of the material.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. The elastic nano particle composite nylon powder for selective laser sintering is characterized in that: the composite nylon powder comprises the following raw materials in parts by weight: 60-90 parts of nylon, 5-20 parts of nano elastic particles, 5-30 parts of reinforcing fibers, 0.1-2 parts of composite antioxidant, 0.2-3 parts of flow assistant and 1-5 parts of coupling agent.
2. The selective laser sintered elastic nanoparticle composite nylon powder of claim 1, characterized in that: the composite nylon powder comprises the following raw materials in parts by weight: 75 parts of nylon, 15 parts of nano elastic particles, 15 parts of reinforcing fibers, 0.1 part of composite antioxidant, 1 part of flow aid and 3 parts of coupling agent.
3. The selective laser sintered elastic nanoparticle composite nylon powder of claim 2, characterized in that: the nylon is one or a mixture of more than two of PA6, PA12, PA11, PA66, PA610, PA612, PA1010, PA1012 and PA 1212; the nano elastic particles are one or a mixture of more than two of nitrile rubber powder, POE particles and SBS particles.
4. The selective laser sintered elastic nanoparticle composite nylon powder of claim 3, characterized in that: the reinforced fiber is one or a mixture of more than two of glass fiber, carbon fiber, needle-shaped wollastonite, silicon carbide and cellulose fiber.
5. The selective laser sintered elastic nanoparticle composite nylon powder of claim 4, characterized in that: the particle size of the fiber is 10-60 mu m.
6. The selective laser sintered elastic nanoparticle composite nylon powder of claim 5, characterized in that: the composite antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants.
7. The selective laser sintered elastic nanoparticle composite nylon powder of claim 6, characterized in that: the hindered phenol antioxidant is one or two of 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 2, 6-di-tert-butyl-4-methyl-phenol; the phosphite antioxidant is one or two of 2 '-ethylbis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylyl diphosphite.
8. The selective laser sintered elastic nanoparticle composite nylon powder of claim 6, characterized in that: the flow auxiliary agent is one or a mixture of more than two of gas-phase silicon dioxide, gas-phase aluminum oxide and nano titanium dioxide; the coupling agent is one or a mixture of more than two of KH550, KH560, KH570, KH792 and DL 602.
9. The method of claim 1 for preparing the elastic nanoparticle composite nylon powder for selective laser sintering, wherein the method comprises the following steps: the method comprises the following steps:
a. adding a coupling agent into a mixture of absolute ethyl alcohol and deionized water, adjusting the pH value to 3-7, stirring at 20-50 ℃ for 30-150min, adding nano elastic particles to prepare a hydrolysis mixture, adding absolute ethyl alcohol, stirring at 50-150r/min for 1-3h, and finally drying at 30-80 ℃; preparing modified nano elastic particles;
b. mixing nylon powder and a solvent, stirring for 20-40min at the temperature of 90-110 ℃, then adding the modified nano elastic particles and the composite antioxidant, stirring for 10-20min, vacuumizing, introducing inert gas, heating to 130-210 ℃ at the heating rate of 1-3 ℃/min, and preserving heat for 0.5-2h after the temperature reaches a set temperature; after the heat preservation time is up, cooling to a set temperature according to the cooling rate of 2-4 ℃/min, finally adding the reinforced fiber, stirring for 0.5-1.5h, cooling to room temperature, and carrying out reduced pressure distillation to prepare composite nylon powder which is coated with the fiber and takes the elastic particles as the inner core;
c. drying and sieving the composite nylon powder to obtain powder with the particle size of less than 100 microns, and then mixing the powder and the flow aid by using a ball mill to obtain the nano elastic particle composite nylon powder.
10. The method of claim 9 for preparing the elastic nanoparticle composite nylon powder for selective laser sintering, wherein the method comprises the following steps: in the step a, the volume ratio of the absolute ethyl alcohol to the deionized water is 8:1-2:1, and the volume ratio of the coupling agent to the mixture of the absolute ethyl alcohol and the deionized water is 1:2-1: 10; adding absolute ethyl alcohol into the hydrolysis mixture according to the volume ratio of 1:20-1: 80.
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